Note: Descriptions are shown in the official language in which they were submitted.
CA 022067~6 1997-06-03
HW/P-20898/A/21059/060/CGC1 ~1
PROCESS FOR PREPARING DIKETOPYRROLOPYRROLE DERIVATIVES
This application relates to a process for preparing 1,4-diketo-3,6-diarylpyrrolopyrrole
derivatives wherein a diketopyrrolopyrrole is reacted with formaldehyde or
paraformaldehyde to yield a 2,5-bis(hydroxymethyl)-3,6-diarylpyrrolopyrrole-1,4-dione which
is isolated or further reacted.
Further, this application relates to a process wherein a 2,5-bis(hydroxymethyl)-3,6-
diarylpyrrolopyrrole-1,4-dione is reacted with a precursor of organic radicals B, and B2, a
process wherein the precursor of the organic radicals B1 and B2 is a 1,4-diketo-3,6-
diarylpyrrolo[3,4-c]pyrrole or a quinacridone, a 2,5-bis(hydroxymethyl)-3,6-
diarylpyrrolopyrrole-1,4-dione, a process for its preparation, a diketopyrrolopyrrole derivative
having two quinacridone radicals as substituents, a diketopyrrolopyrrole derivative having
two diaryldiketopyrrolopyrrole radicals as substituents, a pigment composition, a method of
reducing the viscosity of a dispersion, and a method of preparing a basecoaVclearcoat
finish.
Diaryldiketopyrrolopyrroles of the formula
Al ~
>~~Y
H - N N - H
o A2
wherein A1 and A2 are aryl radicals are well-known as important pigments.
U.S. Patent No. 4,585,878 discloses N-substituted derivatives of the
diaryldiketopyrrolopyrrole pigments, which are useful as polymer soluble dyes or as
pigments, wherein the N-substituent does not confer solubility in water. According to U.S.
Patent No. 4,585,878, the N-substituted derivatives of the diaryldiketopyrrolopyrrole
pigments are prepared by reacting a diaryldiketopyrrolopyrrole compound in an organic
solvent with a compound containing the ultimate N-substituents attached to a leaving group,
or by reacting 2 moles of a compound of the formula R-N=CH-A, wherein R is the N-
substituent and A is an aryl group, or one mole each of two different compounds of the
CA 022067~6 1997-06-03
formula R-N=CH-A, with a succinic acid diester in the presence of a base and an organic
solvent and then dehydrogenating the product.
Rheology-improving agents for organic pigments reduce the viscosity of a dispersion of the
organic pigment in a high-molecular-weight organic material. Some compounds capable of
functioning as rheology-improving agents for organic pigments are known. For example,
phthalimidomethylquinacridone, quinacridone monosulfonic acid salts, especially the
aluminum salt, the dimethylaminopropylsulfonamide derivative of quinacridone andpyrrazolylmethylquinacridone are known rheology improving agents for organic pigments.
Although the known rheology improving agents adequately reduce the viscosity when the
organic pigment is dispersed in a high-molecular-weight organic material, the incorporation
of the known rheology improving agents in a pigment composition based on a bright red or
highly saturated orange pigment generally results in unacceptable pigmentary properties
with significant loss in color and color saturation.
Hence, it was the object of the present invention to provide rheology improving agents
which do not show the abovementioned drawbacks. Preferably, the rheology improving
agents should be based on N-substituted diaryldiketopyrrolopyrroles.
Accordingly a process for the preparation of a diketopyrrolopyrrole derivative of the formula
(I)
A ~ O
~--N ¦ N ~ (I)
~ B2
O A2
was found, wherein A1 and A2 are identical or different aryl radicals and B1 and B2 are
identical or different organic radicals; which diketopyrrolopyrrole derivative contains from O
to 6 moles of -S03M per mole of diketopyrrolopyrrole derivative; wherein M is hydrogen or a
metal or ammonium cation, which process comprises a reaction wherein a 1,4-diketo-3,6-
diarylpyrrolopyrrole of the formula
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Al ~
H - N N- H
~ ~<
o A2
is reacted in a first step with formaldehyde or paraformaldehyde to yield a sulfonated or
non-sulfonated intermediate of the formula
A O
~ OH
rN~ LvN (Il)
1/ \
O A2
which reacts in a second step with a precursor of the organic radicals, B1 and B2, to yield
the diketopyrrolopyrrole derivative of formula (I).
Further, a process, wherein a 2,5-bis(hydroxymethyl)-3,6-diarylpyrrolopyrrole-1,4-dione is
reacted with a precursor of organic radicals B, and B2, a process wherein the precursor of
the organic radicals B1 and B2 is a 1 ,4-diketo-3,6-diarylpyrrolo[3,4-c]pyrrole or a
quinacridone, a 2,5-bis(hydroxymethyl)-3,6-diarylpyrrolopyrrole-1,4-dione, a process for its
preparation, a diketopyrrolopyrrole derivative having two quinacridone radicals as
substituents, a diketopyrrolopyrrole derivative having two diaryldiketopyrrolopyrrole radicals
as substituents, a pigment composition, a method of reducing the viscosity of a dispersion,
and a method of preparing a basecoaVclearcoat finish were found, too.
The present invention relates to a process for preparing a variety of N-substituted
derivatives of diaryldiketopyrrolopyrrole pigments wherein the N-substituents are linked to
the diaryldiketopyrrolopyrrole by -CH2- or -0-CH2- linkages. The inventive process involves
reacting a diaryldiketopyrrolopyrrole with formaldehyde or paraformaldehyde to yield a 2,5-
bis(hydroxymethyl)-3,6-diarylpyrrolopyrrole-1,4-dione intermediate and further reacting the
intermediate, with or without isolation, with a second reactant which reacts with the
hydroxymethyl groups. The products of the reaction are useful as colorants and as
rheology improving agents for pigment dispersions. The 2,5-bis(hydroxymethyl)-3,6-
diarylpyrrolopyrrole-1 ,4-dione intermediate is useful as a synthon for the preparation of a
variety of DPP derivatives, and as a stabilizer for polymers.
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- 4 -
In general, the second reactant reacts with the compound of formula (Il) by a substitution
reaction or to form an -O- linkage.
The first step is preferably carried out by adding the 1,4-diketo-3,6-diarylpyrrolo[3,4-
c]pyrrole to a solution of paraformaldehyde in concentrated sulfuric acid, preferably having
a H2SO4 concentration greater than 90 percent by weight, most preferably above 95 percent
by weight.
In general, the stoichiometric amount of formaldehyde or paraformaldehyde (calculated as
formaldehyde) is used in the first step. Thus, the molar ratio of the 1,4-diketo-3,6-
diarylpyrrolo[3,4-c]pyrrole to the formaldehyde or paraformaldehyde (calculated as
formaldehyde) during the first step usually is in the range of 0.75:2 to 1.25 to 2, preferably
1 :2.
After the first step is complete, the resulting intermediate is reacted with the precursor to
yield the diketopyrrolopyrrole derivative of formula (I).
Preferably, both steps are carried out at a temperature of from 20 to 100~C. If a high
degree of sulfonation is desired, the process is carried out at higher temperatures, for
example above 40~C. If it is desirable to have a low degree of sulfonation, the reaction is
maintained at a lower temperature, preferably 40~C or below.
After the reaction is complete, the 1,4-diketo-3,6-diarylpyrrolo[3,4-c]pyrrole derivative
usually is isolated by procedures conventionally used in the art for isolating 1,4-diketo-3,6-
diarylpyrrolo[3,4-c]pyrroles, in particular by pouring the sulfuric acid solution into ice water
maintaining the temperature below 10~C and stirring the resulting aqueous slurry for about 1
hour, followed by filtration, washing and drying to yield the 1 ,4-diketo-3,6-diarylpyrrolo[3,4-
c]pyrrole derivative in solid form.
Since it is not necessary to isolate the intermediate, the inventive process is preferably a
one pot process. However, it is possible to isolate the intermediate prior to carrying out the
second step, especially, for example, in those instances where it is desired to carry out the
second step in a solvent other than the solvent used for the first step.
CA 022067~6 1997-06-03
Suitable solvents for the second step include concentrated sulfuric acid, polyphosphoric
acid and organic solvents which do not react with the compound of formula (Il), especially
polar organic solvents such as acetonitrile, benzonitrile, dimethylformamide,
dimethylsulfoxide, tetramethylenesulfone.
It is also possible to carry out the second step in a solvent which reacts with the compound
of formula (Il) to yield the desired product, for example, C1-C10 alcohols are suitable solvents
if the compound of formula (I) is the ether obtainable by reacting the compound of formula
(Il) with the alcohol.
In a preferred embodiment of the present invention a 1,4-diketo-3,6-diarylpyrrolopyrrole of
the formula (Il) is reacted with a precursor of the organic radicals, B1 and B2.
Preferably, the diketopyrrolopyrrole derivatives of formula (I) contain from 0 to 4 moles of
-SO3M per mole of diketopyrrolopyrrole derivative; most preferably from 0 to 2 moles per
mole of diketopyrrolopyrrole derivative. In general, if the reaction is carried out at about 40-
50~C, the product contains about 0.5 moles of -SO3M per mole of diketopyrrolopyrrole
derivative.
M is preferably hydrogen, or an alkali metal, such as sodium or potassium, an alkaline earth
metal, such as magnesium, an aluminum, a zinc or an ammonium cation. Examples ofsuitable ammonium cations include quaternary ammonium cations, such as
trimethylcetylammonium or tributylbenzylammonium.
A1 and A2 as aryl include both aromatic and heteroaromatic radicals. Radicals which are
particularly suitable as A1 and A2 include radicals of the formula
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, ~ . ~ N , ~ N ,
~ or ~ G ~ R3
wherein
R1 and R2 are each independently of the other hydrogen, halogen, C1-C18alkyl,
C1-C18alkoxy, C1-C18alkylmercapto, C1-C18alkylamino, C1-C18alkoxycarbonyl,
C1-C18alkylaminocarbonyl, -CN, -NO2, trifluoromethyl, C5-C6cycloalkyl, -CH=N-(C1-C18alkyl),
R4
phenyl, -CH=N ~ = ~ , imidazolyl, pyrrazolyl, triazolyl, piperazinyl, pyrrolyl,
oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, morpholinyl, piperidinyl or
pyrrolidinyl,
Gis-CH2-,-CH(CH3)-,-C(CH3)2-,-CH=N-,-N=N-,-O-,-S-,-SO-,-SO2-,-CONH-or-NR7-,
R3 and R 4 are each independently of the other hydrogen, halogen, C1-C6alkyl,
C1-C~8alkoxy or -CN,R5 and R6 are each independently of the other hydrogen, halogen or
C1-C6alkyl, and R7is hydrogen or C1-C6alkyl.
In particular, A1 and A2 are each a group of formula
~ ~ N , ~or
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R4
G ~ R3
wherein R1 and R2 are each independently of the other hydrogen, chloro, bromo,
C1-C4alkyl, C1-C6alkoxy, C1-C6alkylamino, phenyl or CN,
G is -O-, -NR7-, -N=N- or-S02-,
R3 and R4 are hydrogen, and R7 is hydrogen, methyl or ethyl,
and more particularly A1 and A2 are each a group of formula
~R1~
R2
wherein R1 and R2 are each independently of the other hydrogen, methyl, tert-butyl, chloro,
bromo, phenyl or CN. At least one of R1 and R2 is preferably hydrogen. Most preferably, at
least one of R1 and R2 is hydrogen and the other is in the 3- or 4 position of the phenyl ring.
According to the present invention, the organic radicals B1 and B2 are derivable from a
precursor which reacts with the hydroxy groups of a compound of the formula (Il) either by a
substitution reaction or to form an -O-linkage.
Precursors which react with a hydroxyl group by a substitution reaction are generally
compounds which comprise an aromatic radical, a heteroaromatic radical, or radicals of the
formulae X-C(=O)-Y-, -Y-C(=O)-O-X, X-C(=S)-Y-, -Y-C(=S)-O-X, -Y-C(=S)-S-X, X-C(=N)-Y-,
XZN-, X-~, X-S02-, X-S02-NR10-, ~N - ~ N ~
Rlo~N and -N(R10)-C(=O)-O-X; wherein X and Z are each hydrogen or an
x~O
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-8-
aliphatic, alicyclic, araliphatic, aromatic or heterocyclic radical, or X and Z together form a 3
to 8 membered ring, Y is the residue of an active methylene containing moiety, and R10 is
hydrogen, an aliphatic radical, an alicyclic radical, an araliphatic radical, an aromatic radical
or a heterocyclic radical, or R10 and X together form a 3 to 8 membered ring.
Examples of B~ and B2 radicals derivable from a precursor which reacts with a hydroxyl
group to form an -O-linkage include an alkyl halide and radicals of the formulae X-C(=O)O-,
X-C(=S)O-, X-S02-0-, XO-; wherein X has the meaning given above.
As aromatic radicals, B1 and B2 especially include radicals containing 1, 2, 3, 4 or more
phenyl rings which are bonded directly to each other, bonded to each other through a
linking group, fused, or any combination thereof. The biphenylyl radical is an example of
two phenyl rings directly bonded to each other. Radicals of the formula
~3G1~3 and ,~Gl~¦ wherein G~ is a linking
group, are examples of phenyl rings bonded through each other through a linking group.
Examples of aromatic radicals containing fused phenyl rings include naphthyl, anthryl and
phenanthryl.
The linking group G1 is especially those linking groups described above for the variable G.
As heteroaromatic radicals, B~ and B2 especially include radicals containing one or more 5,
6 or 7 membered aromatic rings containing from 1 to 4 heteroatoms. In general, the
heteroatom(s) are nitrogen, oxygen, sulfur or any combination thereof. Suitable
heteroaromatic radicals include the pyrrolopyrroles, especially the 1,4-diketo-3,6-
diarylpyrrolo[3,4-c]pyrroles and quinacridones.
Preferably, Y is the residue of an active methylene containing moiety. Active methylene
moieties are generally those methylene groups which are linked to an electron withdrawing
substituent, such as a carbonyl or nitrile substitutent. In general, active methylene moieties
participate in a Mannich type or similar reaction. In general, Y is -CHX, -CH2-X,
CA 022067~6 1997-06-03
-(CH=CH)n-CH2-X, wherein n is 1, 2 or 3. When Y is the -CHX- radical, the -CHX- radical is
part of a ring, for example, when B1 or B2 is the X-C(=O)-Y- radical, X and Y can form part
of, for example, a cyclohexanone ring.
X and Z usually are aliphatic, alicyclic, araliphatic, aromatic or heterocyclic radicals.
In general, aliphatic radicals include C,-C,O alkyl, C,-C,O alkenyl, and C,-C,O alkynyl radicals,
including straight and branched chains.
Alicyclic radicals include those moieties containing only one or more nonaromatic
hydrocarbon rings. Important alicyclic radicals include radicals derived from C3-C8
cycloalkanes and C3-C8cycloalkenes. Examples of important alicyclic radicals include
cyclopentyl, cyclohexyl and cycloheptyl. Alicyclic radicals also include those moieties
wherein there is, for example, a -C(=O)- on the ring, such as cyclohexanone.
Araliphatic radicals are those moieties which contain an aliphatic portion and an aromatic -
portion, for example a phenyl or heteroaromatic portion. Examples of araliphatic radicals
include radicals derived from the phenylalkanoic acids, the naphthylalkanoic acids, the
pyridine alkanoic acids, the quinoline alkanoic acids, the indole alkanoic acids, such as
those derived from phenyl acetic acid, phenyl propionic acid, or indole acetic acid.
Aromatic radicals suitable as X and Z include those described above as being useful as B
and B2. The term "aromatic" radical, in this instance, does not include heteroaromatic
radicals.
Heterocyclic radicals contain one or more nonaromatic and/or aromatic rings which contain
one or more heteroatoms; especially 3 to 8 membered rings which contain 1 to 3
heteroatoms, which heteroatoms are especially nitrogen, sulfur and oxygen. The term
heterocyclic radical includes fused ring systems wherein one or more rings contain one or
more heteroatoms. Important heterocyclic radicals include pyridinyl, pyranyl,
tetrahydrofuranyl, morpholino, pyrimidyl, pyrone, oxazine, azepinyl, triazinyl, oxathiazinyl,
pyrroyl, benzofuranyl, piperazinyl, oxathiazolyl, oxadiazolyl, quinolinyl, indolyl, carbazolyl,
xanthenyl, acridinyl, coumarinyl, benzoxazolyl, benzopyrone, quinazolinyl. Heterocyclic
CA 022067~6 l997-06-03
-10-
radicals include those wherein the ring is a lactone or a lactam.
The description of radicals above also defines aliphatic, alicyclic, araliphatic, aromatic and
heterocyclic radicals suitable as R10. When R10 combines with X to form a ring, the ring is
preferably a five or six membered ring.
The aromatic, heterocyclic, aliphatic, alicyclic and araliphatic radicals are unsubstituted (by
any group other than hydrogen) or substituted by one or more, preferably O to 4, customary
substituents.
Customary substituents include hydroxy, carbonyl, halogen, C1-C18alkyl, C1-C18alkoxy,
C1-C18alkylmercapto, C1-C18alkylamino, di(C1-C18alkyl)amino, C1-C18alkoxycarbonyl,
C1-C18alkylaminocarbonyl, -CN, -NO2, trifluoromethyl, C5-C6cycloalkyl, -C=N-(C1-C18alkyl),
phenyl, wherein alkyl groups can be further substituted by hydroxyl, halogen, nitro,
C1-C6alkoxy, carbonyl, -CN.
Substituents defined as halogen are typically iodo, fluoro, bromo and, preferably, chloro;
C1-C6alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-amyl,
tert.-amyl, hexyl, and C1-C10alkyl and C1-C18alkyl are in addition typically heptyl, octyl,
2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl.
C1-C18Alkoxy, also in C1-C18alkoxycarbonyl, is typically methoxy, ethoxy, n-propoxy,
isopropoxy, butoxy, hexyloxy, decyloxy, dodecyloxy, hexadecyloxy or octadecyloxy.
C1-C18Alkylmercapto is, for example, methylmercapto, ethylmercapto, propylmercapto,
butylmercapto, octylmercapto, decylmercapto, hexadecylmercapto or octadecylmercapto.
C1-C18Alkylamino is, also in C1-C18alkylaminocarbonyl, typically methylamino, ethylamino,
propylamino, hexylamino, decylamino, hexadecylamino or octadecylamino.
C5-C6Cycloalkyl is typically cyclopentyl and cyclohexyl.
Important radicals containing the residue of an active methylene, Y, include radicals
CA 022067~6 1997-06-03
derivable from various acetoacetanilides, cyanoacetanilides and benzoylacetanilides, such
as ethylacetoacetate, ethyl malonate, ethyl cyanoacetate, ethyl benzoyl acetate and
malononitrile.
Important radicals of the formula X-C(=O)-O- include esters derivable from C~-C24 aliphatic
acids, such as acetic acid, stearic acid, oleic acid, linoleic acid, acrylic acid, methacrylic acid
or trifluoroacetic acid, a C1-C24araliphatic acid, such as benzoic acid, phenyl acetic acid,
phenyl propionic acid or indole acetic acid, a resin acid, such as abeitic acid, behemic acid,
a naphthenic acid, a dimeric acid, wherein the aliphatic acids and araliphatic acids are
unsubstituted or substituted by one or more customary substituents.
Important radicals of the formula X-C(=O)NR10- and X-S02-NR10- include those derivable
from amides and sulfonamides prepared from an aliphatic amine and an aliphatic carboxylic
or sulfonic acid, an aromatic amine and a aliphatic carboxylic or sulfonic acid, or an
aromatic amine and an aromatic or araliphatic carboxylic or sulfonic acid. Suitable radicals
of the formula X-C(=O)NR10- and X-S02-NR10 especially include those wherein X is C~-
C24 alkyl, phenyl, benzyl, tolyl, naphthyl and R10 is hydrogen, methyl, ethyl, n-propyl,
isopropyl, phenyl, benzyl.
Important radicals of the formulae X-S02-, X-S02-0- and X-C(=S)-O- include thosewherein X is a C~-C24 aliphatic radical, an C6-C1 8 aromatic radical, a C~-C24 araliphatic
radical, a 5, 6 or 7 membered heterocyclic ring, or a fused ring system containing a 5, 6 or 7
membered heterocyclic ring, such as pentyl, hexyl, phenyl, benzyl, tolyl, naphthyl, pyridinyl
or indolyl. Important radicals of the formula X-S02-0- include those derivable from p-
toluene sulfonic acid, naphthalene sulfonic acid, pentane sulfonic acid or a water-soluble
dye which contains a -S03H water-solublizing group.
Important radicals of the formula XZN- include those derivable from N,N-di C,-C24alkyl
amines, such as dimethylamine, diethylamine dipropylamine, and dibutylamine, arylamines,
such as N,N-diphenylamine, aralkylamines, such as N,N-dibenzylamine or
ethylphenylamine, or heteroaryl amines, such as aminopyridine. The formula XZN- also
includes those radicals wherein X and Z, together, along with the nitrogen atom, form a 3 to
8 membered ring, especially a 5 or 6 membered ring, such as a piperazine, morpholine,
CA 022067~6 l997-06-03
-12-
thiomorpholine, pyrrolidine or piperidine ring.
Important radicals of the formulae XO- include those wherein X is a C~-C24 aliphatic radical,
a C5-C10 alicyclic radical, phenyl, benzyl, naphthyl, or a radical H-(CH2CHR~O)m-
CH2CHR~-, wherein R11 is hydrogen or methyl, especially hydrogen, and m is a number
from 1 to 20.
Important radicals of the formula XS- include those wherein X is a C,-C24aliphatic radical, a
C5-C1Oalicyclic radical, phenyl, benzyl and naphthyl.
Importa~ radicals of the formula ~ or
Rl~'~l~N include radicals derivable from succinimide, glutarimide, phthalimide,
XJ~o
naphthalimide and isoquinoline-1,3-dione.
Important radicals of the formula -N(R10)-C(=O)-O-X include those wherein R1o is hydrogen,
C1-C6alkyl, phenyl or benzyl, especially hydrogen and C~-C6alkyl, and X is C1-C6alkyl, for
example, urethane.
Aromatic and heteroaromatic radicals derivable from known dyes, such as azo, azomethine,
or fiber-reactive dyes, for example triazine dyes, or known organic pigments, such as
diketopyrrolopyrrole, quinacridone, phthalocyanine, indanthrone, isoindoline, isoindolone,
flavanthrone, pyranthrone, anthraquinone, thioindigo, perylene and dioxazine pigments are
suitable radicals for B1 and B2. Quinacridinyl (derived from a quinacridone) and 1,4-diketo-
3,6-diarylpyrrolo[3,4-c]pyrrolyl (derived from a 1,4-diketo-3,6-diarylpyrrolo[3,4-c]pyrrole)
radicals are especially suitable radicals for B1 and B2 .
Thus, an aspect of the present invention relates to a process of preparing
diketopyrrolopyrrole derivatives of the formula (I) wherein B1 and B2 are each a pigment
CA 022067~6 l997-06-03
-13-
moiety, in particular, a diketopyrrolopyrrole, quinacridone, phthalocyanine, indanthrone,
isoindoline, isoindolone, flavanthrone, pyranthrone, anthraquinone, thioindigo, perylene and
dioxazine pigment moiety.
1,4-diketo-3,6-diarylpyrrolo[3,4-c]pyrrolyl radicals are especially suitable radicals for B1 and
B2. Such radicals are derivable from compounds of the formula
A ~
H- N N - H
~ ~<
O A2 which are well-known as pigments, preferably
Al ~
>~
H - N N -
~ ~<
o A2 is used as radical.
When B1 and B2 are 1,4-diketo-3,6-diarylpyrrolo[3,4-c]pyrrolyl radicals, the preferences
described above for A1 and A2 apply.
Another aspect of this invention relates to a process for preparing diketopyrrolopyrrole
derivatives of formula (I) wherein B1 and B2 are quinacridinyl radicals. Such radicals are
derivable from the compounds of the formula
R ~ R
O H
wherein each R is independently hydrogen, halogen, carboxyl, unsubstituted C~-C6 alkyl,
C1-C6 alkyl which is substituted by halogen, unsubstituted C1-C6 alkoxy, or C1-C6 alkoxy
which is substituted by halogen.
B, and B2 are especially radicals derivable from quinacridone, 2,9-dichloroquinacridone,
4,11-dichloroqunacridone, 2,9-dimethylquinacridone, 4,11-dimethylquinacridone,
2,9-difluoroquinacridone.
CA 022067~6 l997-06-03
-14-
The present invention also relates to a compound of the formula
Al O
~ OH
rN~N (Il)
O A2
which contains from 0 to 6 moles of -SO3M per mole of the compound, wherein A1 and A2
are identical or different aryl radicals and M is hydrogen or a metal or ammonium cation.
A1 and A2 have the meaning given above.
Preferably A1 and A2 are radicals of the formula
, ~ , ~ N , ~ N ,
O~ ~ G ~ R3 1
wherein
R1 and R2 are each independently of the other hydrogen, halogen, C1-C18alkyl,
C1-C18alkoxy, C1-C18alkylmercapto, C1-C18alkylamino, C1-C18alkoxycarbonyl,
C1-C18alkylaminocarbonyl, -CN, -NO2, trifluoromethyl, C5-C6cycloalkyl, -CH=N-(C1-C18alkyl),
R4
phenyl, -CH=N , imidazolyl, pyrrazolyl, triazolyl, piperazinyl, pyrrolyl,
oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, morpholinyl, piperidinyl or
pyrrolidinyl,
G is -CH2-, -CH(CH3)-, -C(CH3)2-, -CH=N-, -N=N-, -O-, -S-, -SO-, -SO2-, -CONH- or -NR7-,
R3 and R 4 are each independently of the other hydrogen, halogen, C1-C6alkyl,
CA 022067~6 l997-06-03
-15-
C1-C18alkoxy or -CN, Rs and R6 are each independently of the other hydrogen, halogen or
C1-C6alkyl, and R7 is hydrogen or C1-C6alkyl.
In particular, A1 and A2 are radicals of the formula
~R, ~ or
G ~ R3
wherein R~ and R2 are each independently of the other hydrogen, chloro, bromo,
C1-C4alkyl, C1-C6alkoxy, C1-C6alkylamino, phenyl or CN,
G is -O-, -NR7-, -N=N- or -SO2-,
R3 and R4 are hydrogen, and
R7 is hydrogen, methyl or ethyl.
Most preferably, A1 and A2 are radicals of the formula ~R,
R2
wherein R1 and R2 are each independently of the other hydrogen, methyl, tert-butyl, chloro,
bromo, phenyl or CN. Preferably, at least one of R1 and R2 is hydrogen.
Preferably the compounds of formula (Il) have from O to 4 moles of -S03M, most preferably
from O to 2 moles of -S03M.
The present invention further relates to a process for preparing a compound of the formula
CA 022067~6 l997-06-03
-16-
Al O
~ OH
rNh ~N
O A2
which contains from 0 to 6 moles of -SO3M per mole of the compound, wherein A1 and A2
are identical or different aryl radicals and M is hydrogen or a metal or ammonium cation,
which process comprises reacting a 1,4-diketo-3,6-diarylpyrrolopyrrole of the formula
Al ~
H - N N- H
~ ~<
o A2
with formaldehyde or paraformaldehyde.
The preferences discussed above relating to the first step of the process for preparing the
compounds of formula (I) are applicable to this aspect of the invention, too.
In particular, the present invention relates to the process wherein the 1,4-diketo-3,6-
diarylpyrrolopyrrole is combined with paraformaldehyde in concentrated sulfuric acid;
especially wherein the 1,4-diketo-3,6-diarylpyrrolopyrrole and formaldehyde (or
paraformaldehyde, caculated as formaldehyde) are present in a molar ratio in the range of
0.75:2 to 1.25:2, most preferably of about 1:2.
If less sulfonation is desired, the reaction preferably is carried out at a temperature of 40~C
or below. The reaction generally proceeds at higher temperatures, for example, in the
range from about 20 to 1 20~C, but higher temperatures generally lead to a higher degree of
sulfonation; which may be desirable depending on the intended use of the final product.
The hydroxymethyl derivative of formula (Il) is generally isolated by precipitation and
filtration, for example by drowning in an organic solvent or water followed by filtration.
Another preferred aspect of the present invention relates to a diketopyrrolopyrrole derivative
of the formula (la) (B, and B2 = QA)
CA 022067~6 1997-06-03
Al O
~R
QA CH2--N~ ,N--CH2 QA (la)
O A2
wherein A, and A2 are identical or different aryl radicals, having the meaning given above,
and QA is a quinacridone radical; which pyrrolopyrrole derivative is substituted by from O to
6 moles of -SO3M per mole of the pyrrolopyrrole derivative; wherein M is hydrogen or a
metal or ammonium cation as previously defined.
Preferably, the pyrrolopyrrole derivative is substituted with from O to 2 moles of -SO3M per
mole of DPP derivative, most preferably O to 0.75 moles of -SO3M per mole of DPPderivative. Particularly preferred pyrrolopyrrole derivatives contain virtually no -SO3M.
The preferences described above for A1 and A2 apply. In a preferred embodiment of the
present invention A, and A2 are phenyl or 4-tertiarybutylphenyl.
QA is preferably a quinacridone radical of the formula (Ill)
wherein each R is a customary substituent; preferably in the 2 and 9 or 4 and 11 positions.
Preferably, each R is independently hydrogen, halogen, carboxyl, unsubstituted C1-C6alkyl,
C1-C6 alkyl which is substituted by halogen, unsubstituted C1-C6alkoxy, or C1-C6-alkoxy
which is substituted by halogen.
Preferably, QA is a quinacridone radical derivable from quinacridone,
2,9-dichloroquinacridone, 4,11-dichloroquinacridone, 2,9-dimethylquinacridone,
4,11-dimethylquinacridone, 2,9-difluoroquinacridone. Thus, preferred QA substituents are
quinacridone radicals of formula (Ill) wherein each R is hydrogen, Cl, F or -CH3. Preferably,
CA 022067~6 1997-06-03
if both R substituents are not hydrogen, both R substituents are the same and selected
from the group consisting of Cl, F or -CH3 and most preferably in the 2, 9 or 4, 11 positions.
Alternatively, both R substituents are hydrogen.
Especially important compounds are those wherein A1 and A2 are identical and are selected
from the group consisting of phenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-chlorophenyl,
4-bromophenyl and biphenyl-1-yl (4-phenyl-phenyl); especially those compounds wherein
both R substituents on the QA radical of formula (Ill) are hydrogen.
In a particularly preferred embodiment of the present invention, the most preferred
compounds are those pyrrolopyrrole derivatives of formula (la) wherein A1 and A2 are each
a group of formula
~5R1
R2
wherein R1 and R2 are each independently of the other hydrogen, methyl, tert-butyl, chloro,
bromo, phenyl or CN;
and QA is a radical of the formula
~ ~Ç: ' , ~1 (111)
o
wherein the R substituents are hydrogen, 2,9- or 4,11-dichloro, 2,9- or 4,11-difluoro or
2,9- or 4,11-dimethyl.
Another preferred aspect of the present invention relates to a pyrrolopyrrole derivative of
the formula (Ib) (B, and B2 = DPP)
CA 022067~6 l997-06-03
-19-
Al O
DPP CH2 - N ~ N - CH2- DPP (Ib)
O A2
wherein A, and A2 are identical or different aryl radicals, having the meaning given above,
and DPP is a diaryldiketopyrrolopyrrole radical; which diketopyrrolopyrrole derivative is
substituted by from O to 6 moles of -SO3M per mole of the pyrrolopyrrole derivative; wherein
M is hydrogen or a metal or ammonium cation.
Preferably, the pyrrolopyrrole derivative is substituted with from O to 2 moles of -SO3M per
mole of DPP derivative, most preferably O to 0.75 moles of -SO3M per mole of DPPderivative. Particularly preferred pyrrolopyrrole derivatives contain virtually no -SO3M.
Preferably, DPP is a diaryldiketopyrrolopyrrole radical of the formula
A O
H - N N -
~ ~<
o A4
wherein A3 and A4 are aryl radicals and have the same meaning as A1 and A2 which are
defined above.
The preferences described above for A, and A2 apply, too, for A3 and A4.
Preferred compounds are those wherein A, and A2 are identical and are selected from the
group consisting of phenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-chlorophenyl,
4-bromophenyl and biphenyl-1-yl (4-phenyl-phenyl), especially those wherein A3 and A4 are
also identical and selected from the group consisting of phenyl, 4-methylphenyl, 4-tert-
butylphenyl, 4-chlorophenyl, 4-bromophenyl and biphenyl-1-yl.
A preferred class of pyrrolopyrrole derivatives are those wherein A3 and A4 are each
4-tertbutylphenyl; especially those wherein A, and A2 are identical and selected from
phenyl, 4-tertbutylphenyl and 4-methylphenyl; especially 4-tertbutylphenyl. Such
CA 022067~6 1997-06-03
-20-
pyrrolopyrrole derivatives provide excellent rheology improvement properties when
incorporated into a pigment composition, but additionally provide enhancement of desirable
pigment properties such as hiding (opacity) and color saturation. Thus, the pyrrolopyrrole
derivative wherein A1, A2, A3 and A4 are each 4-tertbutylphenyl represents an especially
preferred compound of the present invention.
Another preferred class of pyrrolopyrrole derivatives are those wherein A3 and A4 are each
4-methylphenyl; and A, and A2 are identical and selected from the group consisting of
phenyl, 4-tertbutylphenyl and 4-methylphenyl; especially 4-tertbutylphenyl.
The pyrrolopyrrole derivatives of the present invention are especially suitable for use as
rheology-improving agents for organic pigments. As rheology-improving agents for organic
pigments, the inventive pyrrolopyrrole derivatives function to reduce the viscosity of a
dispersion of the pigment composition in a high-molecular-weight organic material, such as
a coating composition, for example, a water-borne or solvent-borne automotive paint.
Thus, another aspect of this invention relates to pigment compositions which comprise an
organic pigment and a pyrrolopyrrole derivative of formulae (I, la and/or Ib). Preferably, the
pigment composition contains from 0.1 to 20 percent by weight of the pyrrolopyrrole
derivative. Most preferably, the pigment composition contains from 1 to 10 percent by
weight of the pyrrolopyrrole derivative.
Preferably, the pyrrolopyrrole derivative of formulae (I, la and/or Ib) is selected such that A1,
A2, A3 and A4 are each a group of formula
~5R1
R2
wherein R1 and R2 are each independently of the other hydrogen, methyl, tert-butyl, chloro,
bromo, phenyl or CN. At least one of R1 and R2 is preferably hydrogen. Most preferably, at
least one of R1 and R2 is hydrogen and the other is in the 3- or 4-position of the phenyl
rlng.
CA 022067~6 l997-06-03
-21-
lmportant pigment compositions according to the present invention are those which contain
a 1 ,4-diketo-3,6-diarylpyrrolo[3,4-c]pyrrole pigment or a quinacridone pigment as the
organic pigment including their solid solutions and a pyrrolopyrrole derivative of the
formulae (I, la and/or Ib).
The inventive pigment compositions especially include those containing a 1,4-diketo-3,6-
diarylpyrrolo[3,4-c]pyrrole pigment selected from the group consisting of unsubstituted
1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole, 1,4-diketo-3,6-di(3- or 4-chlorophenyl)pyrrolo-
[3,4-c]pyrrole, 1,4-diketo-3,6-di(3,4-dichlorophenyl)pyrrolo[3,4-c]pyrrole, 1,4-diketo-3,6-di-
(3-cyanophenyl)pyrrolo[3,4-c]pyrrole, 1,4-diketo-3,6-di(4-tert-butylphenyl)pyrrolo-
[3,4-c]pyrrole, 1,4-diketo-3,6-di(4-methylphenyl)pyrrolo[3,4-c]pyrrole, and 1,4-diketo-3,6-
di(biphenyl-1-yl)pyrrolo[3,4-c]pyrrole, and a pyrrolopyrrole derivative of formulae (I, la and/or
Ib).
In addition, the inventive pigment compositions especially include those containing a
quinacridone pigment selected from the group consisting of unsubstituted quinacridone,
2,9- and 4,11-dimethylquinacridone, 2,9- and 4,11-dichloroquinacridone and 2,9- and
4,11-difluoroquinacridone and a pyrrolopyrrole derivative of formulae (I, la and/or Ib).
Especially important pigment compositions are those containing a 1,4-diketo-3,6-diarylpyrrolo[3,4-c]pyrrole pigment selected from the group consisting of unsubstituted
1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole and 1,4-diketo-3,6-di(4-tert-butylphenyl)pyrrolo-
[3,4-c]pyrrole in combination with a pyrrolopyrrole derivative of formulae (I,and/or la), and/or
of formula (Ib) wherein A3 and A4 are each 4-tertbutylphenyl, especially those wherein in
addition A1 and A2 are identical and selected from phenyl, 4-tert.butylphenyl and
4-methylphenyl; especially 4-tert.butylphenyl, most preferred, if the organic pigment is red
or orange colored, or wherein A3 and A4 are each 4-methylphenyl, especially those wherein
in addition A1 and A2 are identical and selected from phenyl, 4-tert.butylphenyl and
4-methylphenyl; especially 4-tert.butylphenyl.
Although the pigment compositions of the present invention can consist of only the organic
pigment and the pyrrolopyrrole derivative, the pigment compositions generally contain
customary additives, such as texture improving agents, light stabilizers and especially a
CA 022067~6 1997-06-03
-22-
second rheology-improving agent. In this application, the expression "pigment composition"
preferably means a formulation which is to be dispersed in a high-molecular-weight organic
material that is composed of the pigment, the pyrrolopyrrole derivatives and any optional
additives.
Useful light stabilizers are U.V. Iight absorbers, for example, benzotriazoles or hindered
amine light stabilizers (HALS).
Texture-improving agents are especially useful as an additional component which can
improve the properties of the stir-in pigment compositions. Suitable texture-improving
agents include fatty acids having at least 12 carbon atoms, and amides, esters or salts of
fatty acids. Typical fatty acid derived texture-improving agents include fatty acids such as
stearic acid or behenic acid, and fatty amines such as lauryl amine, or stearylamine. In
addition, polyols, such as aliphatic 1,2-diols or polyvinyl alcohol, and ethoxylated fatty
alcohols, epoxidized soya bean oil, waxes, resin acids and resin acid salts are suitable
texture-improving agents. Rosin acids and rosin acid salts are especially suitable texture-
improving agents. In general, the inventive pigment compositions contain from 0 to 20
percent by weight of the texture improving agent, preferably 0.5 to 10 percent by weight.
Agents useful as the second rheology-improving agent in the present pigment compositions
include quinacridone derivatives, such as, quinacridone sulfonic acid, or a salt thereof,
especially the aluminum salt, or pyrazolylmethylquinacridone, or other pyrrolopyrrole (DPP)
derivatives, such as, a DPP sulfonic acid, or a salt thereof, or a another DPP derivative of
the formula 1. If the pigment composition includes a second rheology-improving agent, the
combined parts by weight of the pyrrolopyrrole derivative of formulae (I, la and/or Ib) and
the second rheology-improving agent are preferably in the range from 0.2 to 20 parts by
weight per part of the pigment; most preferably from 2 to 10 parts per part of the pigment.
As discussed above, the presence of an inventive pyrrolopyrrole derivative in a dispersion
of an organic pigment in a high-molecular-weight organic material effectively reduces the
viscosity of the dispersion. Thus, the present invention further relates to a method of
reducing the viscosity of a dispersion of an organic pigment in a high-molecular-weight
organic material which comprises incorporating an effective viscosity-reducing amount of a
CA 022067~6 1997-06-03
pyrrolopyrrole derivative of formulae (I, la and/or Ib) into the dispersion.
The pyrrolopyrrole derivative of formulae (I, la and/or Ib) is added to the dispersion on its
own, or, preferably, as a component of a pigment composition.
Preferably, the pyrrolopyrrole derivative of formula (Ib) is chosen such that A1, A2, A3 and A4
are each a group of formula
~R1~
R2
wherein R1 and R2 are each independently of the other hydrogen, methyl, tert-butyl, chloro,
bromo, phenyl or CN. At least one of R1 and R2 is preferably hydrogen. Most preferably,
at least one of R1 and R2 is hydrogen and the other is in the 3- or 4-position of the phenyl
ring.
Preferably, the pyrrolopyrrole derivative of formulae (I, la and/or Ib) is present in the
dispersion in an amount in the range from 0.1 to 20 parts by weight per part of the pigment
dispersion. Preferably, the pyrrolpyrrole derivative of formulae (I, la and/or Ib) is present in
the dispersion in an amount in the range from 0.2 to 10 parts by weight per part of the
pigment dispersion. If the pyrrolopyrrole derivative of formulae (I, la and/or Ib) is combined
with a second rheology-improving agent, the combined parts by weight of the pyrrolopyrrole
derivative of formulae (I, la and/or Ib) and the second rheology-improving agent are
preferably in the range from 0.1 to 20 parts by weight per part of the pigment dispersion;
most preferably from 0.2 to 10 parts per part of the pigment dispersion.
The organic pigment is an azo, azomethine, anthraquinone, phthalocyanine, perinone,
perylene, 1,4-diketo-3,6-diarylpyrrolo[3,4-c]pyrrole, thioindigo, isoindoline, isoindolinone,
quinacridone, flavanthrone, indanthrone, anthrapyrimidine and quinophthalone pigments; in
particular a 1 ,4-diketo-3,6-diarylpyrrolo[3,4-c]pyrrole or quinacridone pigment, or a mixture
thereof .
The high-molecular-weight organic materials are, for example, cellulose ethers, cellulose
esters, polyurethanes, polyesters, polycarbonates, polyolefins, polystyrene, polysulfones,
CA 022067~6 1997-06-03
-24-
polyamides, polycycloamides, polyimides, polyethers, polyether ketones, polyvinyl halides,
polytetrafluoroethylene, acrylic and methacrylic polymers, rubber, silicone polymers,
phenol/formaldehyde resins, melamine, formaldehyde resins, urea/formaldehyde resins,
epoxy resins and diene rubbers or copolymers thereof.
The dispersions especially contain a high-molecular-weight organic material which is useful
for heat-curable or cross-linked coatings, for example chemically-reactive coatings,
including stoving finishes which contain the customary binders and which are reactive at
high temperature. Examples of the high-molecular-weight organic materials which are used
in such coatings include acrylic, alkyd, epoxy, phenolic, melamine, urea, polyester,
polyurethane, blocked isocyanate, benzoguanamine or cellulose ester resins, or
combinations thereof. The pigmented, high-molecular-weight organic materials prepared
according to the present process are also useful as air-drying or physically-drying coatings,
for example, conventional lacquers such as those used in the cosmetics industry as nail
varnishes, for example nitrocellulose lacquers.
The present process is particularly suitable for reducing the viscosity of dispersions
containing high-molecular-weight organic materials conventionally employed as finishes in
the automobile industry, especially acrylic/melamine resin, alkyd/melamine resin or
thermoplastic acrylic resin systems, as well as in aqueous-based coating systems.
The use of many of the known viscosity-reducing agents for pigment dispersions often
results in at least some loss of saturation when the pigment dispersion is applied as the
basecoat in a basecoaVclearcoat automotive finish. However, the use of the present
pyrrolopyrrole derivatives of formulae (1, la and/or Ib) as viscosity-reducing agents
suprisingly does not result in loss of saturation when the pigment dispersion is applied as
the basecoat in a basecoaVclearcoat automotive finish, indeed in many instances the
saturation of the finish is increased by the presence of the pyrrolopyrrole derivative of
formulae (1, la and/or Ib).
Thus, the present invention further relates to a method of preparing a basecoaVclearcoat
finish, which comprises the step of applying a dispersion comprising an effective viscosity-
reducing and saturation-enhancing amount of a pyrrolopyrrole derivative of formulae (1, la
CA 022067~6 1997-06-03
-25-
and/or Ib) in a high-molecular-weight organic compound to a substrate; especially wherein
in the compound of formula (Ib) A3 and A4 are each 4-tert-butylphenyl; and A1 and A2 are
identical and selected from the group consisting of phenyl, 4-tertbutylphenyl and
4-methylphenyl; especially 4-tert-butylphenyl.
Another preferred embodiment relates to a method of preparing an basecoaVclearcoat
finish, which comprises the step of applying a dispersion comprising an organic pigment
and an effective viscosity-reducing amount of a pyrrolopyrrole derivative of formulas (I, la,
Ib) in a high-molecular-weight organic compound to a substrate.
A preferred embodiment of the present invention relates to a coating composition, such as
an automotive finish, which comprises a high-molecular-weight organic material, a red- or
orange-colored organic pigment and a pyrrolopyrrole derivative of the formula (Ib) wherein
A3 and A4 are each 4-tertbutylphenyl; especially those wherein A1 and A2 are identical and
selected from phenyl, 4-tertbutylphenyl and 4-methylphenyl; especially phenyl or 4-tert.-
butylphenyl.
In addition, a preferred embodiment of this invention includes a coating composition, which
comprises a high-molecular-weight organic material, a red- or orange-colored organic
pigment and a pyrrolopyrrole derivative of the formula (Ib) wherein A" A2, A3 and A4 are
each phenyl, or A, and A2 are phenyl and A3 and A4 are each 4-tert.-butylphenyl.
Preferably, the red- or orange-colored organic pigment is selected from the group consisting
of unsubstituted 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole and 1,4-diketo-3,6-di(4-tert.-
butylphenyl)pyrrolo[3,4-c]pyrrole.
Preferably, the high-molecular-weight organic material is an acrylic/melamine resin,
alkyd/melamine resin or thermoplastic acrylic resin.
Preferences discussed above for the pyrrolopyrrole derivatives relate to all other aspects of
this invention.
CA 022067~6 1997-06-03
In this application, the expression "automotive finish" is used to describe finishes typically
used for automobiles, such as waterborne and solventborne basecoaVclearcoat finishes.
Such finishes are used for numerous applications other than for automobiles, such as other
motor vehicles, bicycles, and appliances.
In addition to being useful as an intermediate to prepare the diketopyrrolopyrrole derivatives
of formulae (I, la and/or Ib), the hydroxymethyl pyrrolopyrrole compound of formula (Il) is
useful as a stabilizer for polymers.
The diketopyrrolopyrrole derivatives of formulae (I, la and Ib) are useful as colorants, such
as pigments and dyes, for a variety of materials, in particular paints, plastics and inks, and
as additives which influence the rheology characteristics of a pigment composition.
In general, diketopyrrolopyrrole derivatives of formulae (I, la and Ib) with a lower degree of
sulfonation are most suitable as pigments, while those with a higher degree of sulfonation
are useful as dyes and additives.
The following examples further illustrate the preferred embodiments of this invention. In
these examples, all parts given are by weight unless otherwise noted All viscosity
measurements are taken at room temperature.
Example 1: 500 grams of concentrated sulfuric acid (95.28%) are added to a one liter four-
necked flask equipped with a stirrer, a thermometer and a reflux condenser with a drying
tube. 6.2 grams (0.206 moles) of paraformaldehyde are then introduced into the sulfuric
acid followed by 28.8 grams (0.1 moles) of 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole
(unsubstituted DPP) in small portions maintaining the pot temperature below 30~C. The
reaction mixture is stirred at 25+2~C for 2.5 hours and then poured into ice water, filtered,
washed with water until the filtrate is acid free, dried and pulverized to yield2,5-di(hydroxymethyl)-3,6-diphenylpyrrolo[3,4-c]pyrrole-1,4-dione (analysis C20H16N2O4).
Examples 2-5: The bis(hydroxymethyl) DPP compounds disclosed in Table 1 are prepared
by substituting the appropriate substituted DPP for unsubstituted DPP in the process of
Example 1:
CA 022067~6 1997-06-03
Al O
~ OH
r N ~ N (II)
O A2
Table-1
Bishydroxymethyl DPP derivatives
A1 A2 Mol. Form Mol. Wtcrystallizedfrom
4-CI-phenyl 4-CI-phenyl C20H,4C12N2O4 417 DMF-MeOH
p-tolyl p-tolyl C22H20N204 376 DMF-MeOH
4-t-butyl- t-butyl-phenyl C28H32N204 460 DMF-MeOH
phenyl
biphenyl-1-ylbiphenyl-1-ylC32H24N204 500 DMF-MeOH
Example 6: 250 grams of concentrated sulfuric acid (96%) are added to a one liter four-
necked flask equipped with a stirrer, a thermometer and a reflux condenser with a drying
tube. 14.4 grams (0.05 moles) of 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole (unsubstituted
DPP) are added in small portions maintaining the pot temperature below 25~C. 3.1 grams
(0.103 moles) of paraformaldehyde are then introduced into the reaction mixture. The
reaction mixture is stirred at 25+2~C for four hours and then poured into ice water, filtered,
washed with water until the filtrate is acid free, dried and pulverized to yield2,5-di(hydroxymethyl)-3,6-diphenylpyrrolo[3,4-c]pyrrole-1,4-dione (analysis C20H16N204).
Example 7: 401.2 grams of concentrated sulfuric acid (96%) are added to a one liter four-
necked flask equipped with a stirrer, a thermometer and a reflux condenser with a drying
tube. 17.85 grams (0.05 moles) of 1,4-diketo-3,6-di(4-chlorophenyl)pyrrolo[3,4-c]pyrrole
(dichloro DPP) are added in small portions maintaining the pot temperature below 30~C.
3.1 grams (0.103 moles) of paraformaldehyde are then introduced into the reaction mixture.
The reaction mixture is stirred at 25+2~C for four hours and then poured into ice water,
filtered, washed with water until the filtrate is acid free, dried and pulverized to yield
CA 022067~6 1997-06-03
2,5-di(hydroxymethyl)-3,6-di(4-chlorophenyl)pyrrolo[3,4-c]pyrrole-1,4-dione (analysis
C2oH14CI2N204)
Example 8: 422.9 grams of concentrated sulfuric acid (96%) are added to a one liter four-
necked flask equipped with a stirrer, a thermometer and a reflux condenser with a drying
tube. 22.0 grams (0.05 moles) of 1,4-diketo-3,6-di(biphenyl-1-yl)pyrrolo[3,4-c]pyrrole
(biphenylyl DPP) are added in small portions maintaining the pot temperature below 30~C.
3.1 grams (0.103 moles) of paraformaldehyde are then introduced into the reaction mixture.
The reaction mixture is stirred at 25_2~C for four hours and then poured into ice water,
filtered, washed with water until the filtrate is acid free, dried and pulverized to yield
2,5-di(hydroxymethyl)-3,6-di(biphenyl-1-yl)pyrrolo[3,4-c]pyrrole-1,4-dione (analysis
C32H24N204)-
Example 9: 250 grams of concentrated sulfuric acid (96%) are added to a one liter four-
necked flask equipped with a stirrer, a thermometer and a reflux condenser with a drying
tube. Quinacridone (31.2 grams, 0.1 moles) is added in small portions followed by 14.4
grams (0.05 moles) of 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole (unsubstituted DPP)
maintaining the pot temperature between 40-45~C. After stirring for 0.5 hours, 3.1 grams
(0.103 moles) of paraformaldehyde are then introduced into the reaction mixture and the
temperature rises to about 50~C. The reaction is stirred at 45+3~C for 1 hour and then
poured into ice water, filtered, washed with water until the filtrate is acid free, dried and
pulverized to yield the compound of the formula
Al O
B~
--N ~ ~ ~N ~ (I) wherein A1 and A2 are each
B2
O A2
phenyl and B1 and B2 are quinacridinyl radicals. The product analyzes C6~H3s.5N6O
(S~3H)0.5.
Example 10: 250 grams of concentrated sulfuric acid (96%) are added to a one liter four-
necked flask equipped with a stirrer, a thermometer and a reflux condenser with a drying
tube. 14.4 grams (0.05 moles) of 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole (unsubstituted
CA 022067~6 1997-06-03
- 29 -
DPP) are then added in small portions maintaining the pot temperature below 40~C. After
stirring for 0.5 hours, 3.1 grams (0.103 moles) of paraformaldehyde are then introduced into
the reaction mixture and the temperature rises to about 45~C. The reaction is stirred at
40+2~C for 1 hour. 31.2 grams of quinacridone (0.1 moles) of quinacridone is then added
maintaining the temperature below 45~C. The reaction mixture is stirred at 45+2~C for 3
hours and then poured into ice water, filtered, washed with water until the filtrate is acid
free, dried and pulverized to yield the compound of the formula
Al O
~----N ~ N ~ B2 (I) wherein B, and B2 are
O A2
quinacridinyl radicals. The product analyzes C60H3s.sN6o6 ~ (SO3H)0.5.
Example 11: 250 grams of concentrated sulfuric acid (96%) are added to a one liter four-
necked flask equipped with a stirrer, a thermometer and a reflux condenser with a drying
tube. 14.4 grams (0.05 moles) of 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole (unsubstituted
DPP) are then added in small portions maintaining the pot temperature below 25~C. After
stirring for 1 hour, 3.1 grams (0.103 moles) of paraformaldehyde are then introduced into
the reaction mixture followed by 31.2 grams of quinacridone (0.1 moles) and the
maintaining the temperature below 25~C. The reaction mixture is stirred at 25+2~C for 3
hours and then poured into ice water, filtered, washed with water until the filtrate is acid
free, dried and pulverized to yield the compound of the formula
~ N ~ ~ (I) wherein B1 and B2 are
O A2
quinacridinyl radicals. The product analyzes C60H36N606.
Example 12: 400 grams of concentrated sulfuric acid (96%) are added to a one liter four-
necked flask equipped with a stirrer, a thermometer and a reflux condenser with a drying
tube. 14.4 grams (0.05 moles) of 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole (unsubstituted
CA 022067~6 l997-06-03
-30-
DPP) are then added in small portions maintaining the pot temperature below 25~C. After
stirring for 1 hour, 3.1 grams (0.103 moles) of paraformaldehyde are then introduced into
the reaction mixture followed by 38.1 grams of 4,11-dichloroquinacridone (0.1 moles) and
the maintaining the temperature below 45~C. The reaction mixture is stirred at 45+2~C for
2.5 hours and then poured into ice water, filtered, washed with water until the filtrate is acid
free, dried and pulverized to yield the compound of the formula
A O
~ N ~ N ~ B2 (I) wherein B1 and B2 are
O A2
4,11-dichloroquinacridinyl radicals. The product analyzes CôoH34c12N6o6~
Example 13: 500 grams of concentrated sulfuric acid (90%) are added to a one liter four-
necked flask equipped with a stirrer, a thermometer and a reflux condenser with a drying
tube. 6.2 grams (0.206 moles) of paraformaldehyde are then introduced into the sulfuric
acid followed by 28.8 grams (0.1 moles) of 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole
(unsubstituted DPP) in small portions maintaining the pot temperature below 30~C. The
reaction mixture is stirred at 25+2~C for 2.5 hours and then poured into ice water, filtered,
washed with water until the filtrate is acid free, dried and pulverized to yield a mixture of
2,5-di(hydroxymethyl)-3,6-diphenylpyrrolo[3,4-c]pyrrole-1,4-dione and the starting materials.
When 85% H2SO4 replaces the 90% H2SO4~ a mixture containing a major portion of the
starting materials is obtained.
Example 14: 250 grams of concentrated sulfuric acid (96%) and paraformaldehyde (3.3g.;
0.11 moles) are added to a one liter four necked flask, equipped with a stirrer, a
thermometer, a reflux condenser with a drying tube. Unsubstituted DPP(14.4g.; 0.05moles)
are added to the sulfuric acid/paraformaldehyde mixture in small portions maintaining the
pot temperature between 25-30 ~C. This mixture is stirred for 1 hour to ensure complete
solution. An additional 200g of sulfuric acid is then added to the reaction mixture followed
by unsubstituted DPP(28.8g.; 0.1 moles) in small portions, maintaining the pot temperature
at 32-34~C. This reaction mixture is then stirred at 30+3~C for 4 hrs and poured into ice-
water, filtered, washed with water until the filtrate is acid free, dried and pulverized.
CA 022067~6 l997-06-03
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The compound isolated analyzed for C56H36N606 and is believed to have the formula IV
H
wherein each R and R, substituent is hydrogen.
The compounds in Table 2 are made by substituting the appropriate pyrrolopyrrolereactants in the process of Example 14.
CA 022067~6 1997-06-03
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TABLE 2
DPP-CH2-DPP-CH2-DPP derivatives
R R1 Mol. Form crystallized from
H H C56H36N606 H2S04
H Cl Cs6H32CI4N606 H2S04
H CH3 C60H44N606 H2S04
H t-Butyl C72H6aN606 H2S04
H 4-Phenyl C80H52N606 H2S04
Cl H C56H34C12N606 H2S04
Cl Cl C56H30C16N606 H2S04
Cl CH3 C60H42C12N606 H2S04
Cl t-Butyl C72H66C12N606 H2S04
Cl 4-PhenylC80H50C12N606 H2SO4
CH3 H C58H40N606 H2S04
CH3 Cl C58H36C14N606 H2S04
CH3 CH3 C62H48N606 H2S04
CH3 t-Butyl C74H72N606 H2S04
CH3 4-Phenyl C82H56N606 H2S04
t-Butyl H C64H52N606 H2S04
t-Butyl Cl C64H48CI4N606 H2S04
t-Butyl CH3 C68H60N606 H2S04
t-Butyl t-Butyl C80H84N606 H2SO4
t-Butyl 4-Phenyl C88H68N606 H2SO4
4-Phenyl H C68H44N606 H2SO4
4-Phenyl Cl C68H40C14N606 H2SO4
4-Phenyl CH3 C72H52N606 H2S04
4-Phenyl t-Butyl C84H76N606 H2SO4
4-Phenyl 4-Phenyl Cg2H60N606 H2S04
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Example 15: 250 grams of concentrated sulfuric acid (96%) and paraformaldehyde (3.3g.;
0.11 moles) are added to a one liter four necked flask, equipped with a stirrer, a
thermometer, a reflux condenser with a drying tube. Unsubstituted DPP(14.4g.; 0.05moles)
are added to the sulfuric acid/paraformaldehyde mixture in small portions maintaining the
pot temperature between 30-35 ~C. This mixture is stirred for 1 hour to ensure complete
solution. An additional 200g of sulfuric acid is then added to the reaction mixture followed
by unsubstituted DPP(28.8g.; 0.1 moles) in small portions, maintaining the pot temperature
at 38-42 ~C. This reaction mixture is then stirred at 40+3~C for 4 hrs and poured into ice-
water, filtered, washed with water until the filtrate is acid free, dried and pulverized.
The compound isolated analyzed for C56H36N6O6-(SO3H)0 5
The sulfonated derivatives of the compounds of Table 2 are prepared by substituting the
appropriate pyrrolopyrrole reactants in the process of Example 15.
Example 16: Bishydroxymethyl DPP (17.4g, 0.05 moles), aniline (9.3g, 0.1moles) and DMF
(100ml) are added to a one liter four necked flask, equipped with a stirrer, a thermometer,
and a reflux condenser with a drying tube. The mixture is stirred at 100~C for 4 hrs, then
diluted with water, filtered, washed with water, dried and pulverized to give
2,5-di(anilinomethyl)-3,6-diphenyl pyrrolo[3,4-c]pyrrole-1,4-dione (bisanilinomethyl DPP).
Example 17: Bishydroxymethyl DPP (17.4g, 0.05 moles), a catalytic amount of paratoluene
sulfonic acid and methanol (100ml) are added to a one liter four necked flask, equipped
with a stirrer, a thermometer, and a reflux condenser with a drying tube. The mixture is
stirred at reflux for 4 hrs., diluted with water, filtered, washed with water, dried and
pulverized to give 2,5-di(methoxymethyl)-3,6-diphenyl pyrrolo[3,4-c]pyrrole-1,4-dione
(bismethoxymethyl DPP).
Example 18: Bishydroxymethyl-di-t-butyl DPP (23.0g, 0.05 moles), a catalytic amount of
paratoluene sulfonic acid and methanol (100ml) are added to a one liter four necked flask,
equipped with a stirrer, a thermometer, and a reflux condenser with a drying tube. The
mixture is stirred at reflux for 4 hrs, diluted with water, filtered, washed with water, dried and
pulverized to give 2,5-di(methoxymethyl)-3,6-di-t-butylphenyl pyrrolo[3,4-c]pyrrole-1,4-dione
CA 022067~6 1997-06-03
- 34 -
(bismethoxymethyl di-t-butyl DPP).
Examples 19-26: The following compounds, wherein A" A2 and R are defined according to
formulae (la) and (Ill), are prepared according to the procedures of Examples 9-12 by
substituting the appropriate DPP and quinacridone compounds:
Ex A1 A2 R
19 phenyl phenyl 2,9-diCI
phenyl phenyl 2,9-diMe
21 phenyl phenyl 4,11-diMe
224-tbu-phenyl 4-tbu-phenyl 2,9-diCI
23 4-CI-phenyl 4-CI-phenyl H
24 4-Me-phenyl 4-Me-phenyl H
254-tbu-phenyl 4-tbu-phenyl H
26 4-Me-phenyl 4-Me-phenyl 2,9-diCI
Example 27: A pigment composition is prepared by adding a surface treating agent which
consists of the pyrrolopyrrole derivative of formula (la), alone, or combined with a second
rheology-improving agent, to an aqueous suspension of the pigment, filtering and washing
to yield the pigment composition. The viscosity of a dispersion of the pigment composition
in a commercial high solids solvent-borne paint formulation is measured at 50 rpm.
CA 022067~6 1997-06-03
-35-
Pyrrolopyrrole Second Rheology Pigment % byWeight P/B Millbase
DerivativeImproving Agent Pigment in Viscosity
Dispersion (Brookfield)
none none 1 10 0.5 1610
8% Example 11 none 1 100.5 63
4% Example 11 4% QMA 1 100.5 62
4% Example 24 4% PMQA 2 100.5 600
4% Example 19 4%PMQA 2 100.5 708
4% Example 22 4% PMQA 2 100.5 648
4% Example 25 4% PMQA 2 100.5 474
4% Example 10 4% QMA 2 100.5 736
none none 3 10 0.5 1910
4% Example 10 4% QMA 3 100.5 1210
QMA=quinacridone sulfonic acid, aluminum salt
PMQA=pyrrazolylmethylquinacridone
= a ternary solid solution of dichloro DPP/DPP/2,9-dichloroQA (48132120)
2=binary solid solution of dichloro DPP/2~s-dichlOrOQA(60/40
8=1 ,4-diketo-3,6-di(biphenyl-1 -yl)pyrrolopyrrole
Example 28: A solid solution of dichloro DPP/dichloroquinacridone (40/60) is prepared by
milling a mixture of the two individual components on a roller for 24 hours and stirring the
mill powder with 2% sulfuric acid for 2 hours at 90~C, and then filtering and washing the
resulting pigment slurry. The resulting presscake is reslurried in water and combined with
the rheology-improving agent(s) specified in the table below, filtered, washed, dried and
pulverized to yield a treated pigment. A pigment dispersion containing 10% pigment and
30% solids at a pigmenVbinder ratio of 0.5 is prepared by combining the treated pigment
with acrylourethane resin, dispersant resin and solvent and milling with grinding media for
64 hours. The Brookfield viscosity of the resulting pigment dispersion is reported in the
following table.
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- 36 -
PyrrolopyrroleSecond RheologyMillbase
DerivativeImproving Agent Viscosity
(Brookfield)
4% Example 104% PQMA 566
4% Example 244% PQMA 600
4% Example 254% PQMA 474
4% Example 264% PQMA 708
4% Example 224% PQMA 648
Example 29: Automotive finishes are obtained by spray painting aluminum panels with a
metallic or mica paint formulation prepared by conventional methods and pigmented with
the above described pigment compositions. The coatings exhibit attractive, intense colors
with excellent two-tone, high gloss and distinctness of image.
Example 30: An organic ternary solid solution pigment which is composed of dichloro DPP/-
unsubstituted DPP / 2,9-dichloroquinacridone (48% / 32% / 20%), is combined with a
rheology-improving agent composed of 4% quinacridone monosulfonic acid, aluminum salt
(QMA) and 4% of the pyrrolopyrrole derivative of Example 14 by adding the rheology-
improving agent to an aqueous suspension of the pigment, filtering and washing to yield the
pigment composition. Rheology profiles of pigment dispersions in a commercial high solids
solvent-borne paint formulation containing about 12% by weight of the pigment at a pigment
to binder ratio of 0.5% are depicted in the Table 3.
Table 3
MILLBASE VISCOSITY (BROOKFIELD)
Paint System: BC / CC; % Pigment: 12.0 %; P / B = 0.5
Sample ID Rheology-improving Agent 50 RPM
30a Untreated 3660
30b 4%QMA+4% Example 14 R=R1=H 828
Example 31: An orange-colored di(t-butylphenyl)-DPP pigment is combined with a rheology-
improving agent described according to formula (IV) given in ex.14. Rheology profiles of
CA 022067~6 1997-06-03
pigment dispersions in a commercial high solids solventborne paint formulation containing
about 16% by weight of the pigment at a pigment to binder ratio of 0.5% measured after 4
hours of attritor milling are depicted in the Table 4.
Table 4
Millbase Viscosity (Brookfield)
sample Rheology-improving Agent 50 rpm
31a4% R=H; R,=CH3 868
31b8% R=H; R,=CH3 546
31c4% R=t-Bu, R,=t-Bu 670
31 d8% R=t-Bu, R,=t-Bu 528
The rheology-improving of examples 31 c and 31 d, in addition to the rheology
improvements, improves the color saturation of the pigment when sprayed on a panel as
part of a conventional basecoaVclearcoat automotive finish. Similarly improved co!or
saturation is observed when a different red or orange pigment, for example quinacridone, is
used in place of di(t-butylphenyl)-DPP.
Example 32: An orange-colored di(t-butylphenyl)-DPP pigment is combined with the mixture
of rheology-improving agents described in the Table 5 with R and R, being described
according to formula (IV) given in ex. 14 and PYMQ being pyrrazolylmethylquinacridone.
Rheology profiles of pigment dispersions in a commercial high solids solventborne paint
formulation containing about 16% by weight of the pigment at a pigment to binder ratio of
0.5% measured after 4 hours of attritor milling are depicted in the Table 5.
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- 38 -
Table 5
Millbase Viscosity (Brookfield)
SampleRheology-improving Agent 50rpm
32no treatment >2000
32a 4%PYMQ 954
+
4% R=H; R,=CH3
32b 4% R=H, R,=tBu 1080
+
4% R=H; R1=CH3
32c 2% R=H, R1=tBu 1320
+
2% R=H; R~= CH3
